Reinvestigation of the Oxidation of Organic Contaminants by Fe(Vi): Kinetics and Effects of Water Matrix Constituents

Since previous studies mostly ignored the contributions of Fe(IV) and Fe(V) during the determination of reaction rate constants of ferrate (Fe(VI)) with trace organic contaminants (TrOCs), the intrinsic oxidation ability of Fe(VI) was overestimated. For the first time, this study systemically evaluated the reactivity of Fe(VI) towards four kinds of TrOCs by blocking Fe(IV)/Fe(V) over the TrOCs degradation, and evaluated the effects of coexisting water matrix constituents. Results revealed that Fe(VI) exhibited superior reactivity towards phenolic compounds. Different from other tested TrOCs, phenolic compounds were mainly degraded by Fe(VI) rather than Fe(IV)/Fe(V). Taking bisphenol A (BPA) as the target TrOC, we found that the coexisting constituents can not only affect the reactivity of different ferrate species (i.e., Fe(IV), Fe(V), and Fe(VI)), but also alter the concentrations of ferrates. HPO42- inhibited the reaction between Fe(VI) and H2O2, while Ca2+, Mg2+, and NH4+ promoted the generation of Fe(IV)/Fe(V) from Fe(VI). Besides, humic acid could increase the contribution of Fe(IV)/Fe(V) to the oxidation of BPA. These findings were validated in real water samples. Taken together, this study provides a new perspective regarding the intrinsic oxidation reactivity of Fe(VI), thereby urging reconsideration of the proper strategies for utilization of high-valent Fe species in practices.